CN103785346B - A kind of metal traps and its preparation method and application and a kind of catalyst cracking method - Google Patents
A kind of metal traps and its preparation method and application and a kind of catalyst cracking method Download PDFInfo
- Publication number
- CN103785346B CN103785346B CN201210420770.2A CN201210420770A CN103785346B CN 103785346 B CN103785346 B CN 103785346B CN 201210420770 A CN201210420770 A CN 201210420770A CN 103785346 B CN103785346 B CN 103785346B
- Authority
- CN
- China
- Prior art keywords
- metal
- oxide
- pore volume
- aluminium oxide
- traps
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention provides a kind of metal traps and its preparation method and application, this metal traps contains magnesia, have the aluminium oxide of stepped pore distribution and lanthanide rare metal oxide and/or transition metal oxide, and aluminium oxide and at least part of magnesia form magnesia-alumina spinel structure at least partly; The described aluminium oxide with stepped pore distribution contains macroporous aluminium oxide and little porous aluminum oxide; With the pore volume in 2-100nm hole for benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-35%, and the pore volume in 5-10nm hole accounts for 25-45%, and the pore volume in 10-60nm hole accounts for 20-50%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%.The invention provides a kind of catalyst cracking method.Metal traps provided by the invention is used for high vanadium RFCC, the destruction of vanadium to Cracking catalyst can be slowed down, improve liquid product yield, reduce dry gas and coking yield.
Description
Technical field
The present invention relates to the preparation method of a kind of metal traps and a kind of metal traps, and the application of metal traps in catalytic cracking and a kind of catalyst cracking method.
Background technology
The constantly soaring of crude oil price has increased considerably the processing cost of refinery, at present, catalytic cracking is the important means of refinery heavy oil processing, in order to reduce costs to make maximizing the benefits, and poor oil can be used to carry out processing realizing by deep processing mink cell focus.
But, higher heavy metal (as the vanadium) content of crude oil with poor quality.Vanadium-containing compound in oil is the metal complex that a class is very complicated, generally exists with the form of porphyrin vanadium and non-porphyrin vanadium.Metalloporphyrin boiling point generally, between 565-650 DEG C, mainly concentrates in residual oil, but because of its volatility comparatively strong, also can enter in catalytic cracking cut.Non-porphyrin metal compound may be the compound that the relative molecular weight together with molecular association large with asphalitine is less than 400, and its part may be 4N, NO
2s or 4S; After the macromolecular three-dimensional structure of asphalitine is destroyed, these Small molecular will be released.Vanadium to the pollution of catalytic cracking catalyst mainly vanadium irreversible destruction is caused to catalyst.Experiment shows, vanadium poising agent depositing 1000 μ g/g is enough to cause damage to zeolite, worsens product slates.
Usually metal traps is used to carry out the trapping of heavy metal, to reduce heavy metal (as vanadium) to the destruction of Cracking catalyst at present.Spinelle is conventional metal traps material, and as US5603823A discloses a kind of vanadium trapping agent, it consists of the MgO of (a) 15-60w%, the Al of (b) 30-60w%
2o
3and the rare earth of (c) 10-30w%, rare earth is selected from lanthanum-oxides and/or neodymium oxides, wherein, and at least part of MgO and Al
2o
3define Mg-Al spinelle.
CN1148256C discloses a kind of composition and method of making the same containing magnesium aluminate spinel, said composition contains the magnesia of the heavy % of 25-30, the aluminium oxide of the heavy % of 60-70 and the rare-earth oxide except cerium of the heavy % of 5-15, wherein, magnesium and aluminium form spinel structure, the content of free magnesium weighs % lower than 5 of total composition, and the most probable bore dia of described composition is not less than 10nm.
Summary of the invention
The object of the invention is to provide one to have adsorption rate on the basis of existing technology fast, and there is metal traps of excellent metal trapping performance and its preparation method and application.
For realizing aforementioned object, on the one hand, the invention provides a kind of metal traps, this metal traps contains magnesia, have the aluminium oxide of stepped pore distribution and lanthanide rare metal oxide and/or transition metal oxide, and aluminium oxide and at least part of magnesia form magnesia-alumina spinel structure at least partly;
Wherein, the aluminium oxide described in stepped pore distribution contains macroporous aluminium oxide and little porous aluminum oxide; With the pore volume in 2-100nm hole for benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-35%, and the pore volume in 5-10nm hole accounts for 25-45%, and the pore volume in 10-60nm hole accounts for 20-50%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%.
On the other hand, the invention provides a kind of preparation method of metal traps, wherein, the method comprises:
(1) little porous aluminum oxide, deionized water and sour mixed pulp are obtained the first slurries;
(2) described first slurries are contacted with magnesium hydroxide and/or magnesia obtain the second slurries;
(3) described second slurries are contacted with macroporous aluminium oxide obtain the 3rd slurries;
(4) roasting is carried out after described 3rd slurries being carried out spraying dry;
Wherein, with the pore volume in 2-100nm hole for benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-35%, and the pore volume in 5-10nm hole accounts for 25-45%, and the pore volume in 10-60nm hole accounts for 20-50%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%;
Wherein, the mixed pulp of step (1) and/or the first slurries of step (2) and magnesium hydroxide and/or magnesianly to contact and/or step (3) the contact of described second slurries and macroporous aluminium oxide is carried out under the existence of at least one lanthanide metal compound and/or at least one transistion metal compound, and/or contact by the solid obtained after step (4) spraying dry and/or by the solid obtained after step (4) roasting with at least one lanthanide metal compound and/or at least one transistion metal compound before roasting.
Again on the one hand, the invention provides a kind of metal traps adopting the preparation method of metal traps of the present invention to prepare.
Again on the one hand, the invention provides the application of a kind of metal traps of the present invention in catalytic cracking.
Again on the one hand, the invention provides a kind of catalyst cracking method, the method comprises: under catalytic cracking condition, is contacted by heavy oil feedstock with containing metal traps with the catalyst mixture of catalytic cracking catalyst, wherein, described metal traps is metal traps of the present invention.
Metal traps of the present invention has good metal trapping effect, metal traps provided by the invention is used for high vanadium RFCC, can slows down the destruction of vanadium to Cracking catalyst, improve liquid product yield, reduce dry gas and coking yield.Such as, when metal traps provided by the invention mixes by weight for 3:97 with industrial cracking catalyst, on catalyst mixture, Ni content is about 2000ppm, content of vanadium is when being about 4500ppm, with be used alone compared with industrial cracking catalyst, heavy oil yield is reduced to 10.36 % by weight by 12.36 % by weight, total liquid product yield is increased to 74.15 % by weight by 71.60 % by weight, and dry gas selectivity is down to 0.0338 by 0.0358, and coke selectivity is down to 0.1798 by 0.1910.As can be seen here, heavy oil transformation more effectively can be become high-value product by metal traps provided by the invention.
Other features and advantages of the present invention are described in detail in detailed description of the invention part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, is used from explanation the present invention, but is not construed as limiting the invention with detailed description of the invention one below.In the accompanying drawings:
Fig. 1 is the pore size distribution figure of macroporous aluminium oxide A used in the present invention, little porous aluminum oxide A;
Fig. 2 be the metal traps A1 prepared according to the method for the embodiment of the present invention 1 fresh state (being called fresh dose in figure) and in 800 DEG C, hydrothermal aging (was called hydrothermal aging agent) after 17 hours in figure under 100% water vapour atmosphere pore size distribution figure;
Fig. 3 be the metal traps B1 prepared according to the method for comparative example 1 fresh state (being called fresh dose in figure) and in 800 DEG C, hydrothermal aging (was called hydrothermal aging agent) after 17 hours in figure under 100% water vapour atmosphere pore size distribution figure;
Fig. 4 is the metal traps A1 for preparing according to the method for the embodiment of the present invention 1 and the XRD spectra of metal traps B1 prepared according to the method for comparative example 1;
Detailed description of the invention
Below the specific embodiment of the present invention is described in detail.Should be understood that, detailed description of the invention described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
The invention provides a kind of metal traps, this metal traps contains magnesia, have the aluminium oxide of stepped pore distribution and lanthanide rare metal oxide and/or transition metal oxide, and aluminium oxide and at least part of magnesia form magnesia-alumina spinel structure at least partly;
Wherein, the aluminium oxide described in stepped pore distribution contains macroporous aluminium oxide and little porous aluminum oxide; With the pore volume in 2-100nm hole for benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-35%, and the pore volume in 5-10nm hole accounts for 25-45%, and the pore volume in 10-60nm hole accounts for 20-50%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%.
According to metal traps of the present invention, under preferable case, with the pore volume in 2-100nm hole for benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-30%, and the pore volume in 5-10nm hole accounts for 25-40%, and the pore volume in 10-60nm hole accounts for 25-45%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%, and remaining is the pore volume content in 60-100nm hole; More preferably in situation, with the pore volume in 2-100nm hole for benchmark, in described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 52-68%, the pore volume in 5-10nm hole accounts for 15-30%, the pore volume in 10-60nm hole accounts for 11-18%, with the volume in 2-100nm hole for benchmark, in described macroporous aluminium oxide, the pore volume in 60-100nm hole is preferably more than 10%, and in described little porous aluminum oxide, the pore volume in 60-100nm hole is no more than 5%.In the present invention, the hole of described 2-5nm refers to that aperture is more than or equal to 2nm, be less than the hole of 5nm, the hole of 5-10nm, refer to the hole that aperture is more than or equal to 5nm and is less than 10nm, the hole of 10-60nm refers to that aperture is more than or equal to 10nm, is less than the hole of 60nm, and 2-100nm refers to the hole that aperture is more than or equal to 2nm and is less than or equal to 100nm.
In the present invention, the BET specific surface area of preferred described macroporous aluminium oxide is not less than 350m
2g
-1, pore volume is preferably not less than 0.70mLg
-1.
In the present invention, pore size distribution, aperture, pore volume adopt low-temperature nitrogen adsorption method to measure (see " Petrochemical Engineering Analysis method (RIPP test method) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publication).
The aluminium oxide (comprising described macroporous aluminium oxide and described little porous aluminum oxide) described in of the present invention with stepped pore distribution also has detailed introduction in Chinese patent CN101745417B.The present invention quotes for illustration of the present invention in the lump at this.
According to metal traps of the present invention, the described macroporous aluminium oxide and the little porous aluminum oxide that meet application claims can be obtained by synthesis, also can be commercially available, the present invention to this without particular/special requirement.
According to metal traps of the present invention, the aluminium oxide preferably with stepped pore distribution contains the macroporous aluminium oxide of 10-90 % by weight and the little porous aluminum oxide of 10-90 % by weight; The aluminium oxide more preferably with stepped pore distribution contains the macroporous aluminium oxide of 15-85 % by weight and the little porous aluminum oxide of 15-85 % by weight.
According to metal traps of the present invention, as long as ensure that the aluminium oxide described in containing in metal traps of the present invention with stepped pore distribution can well realize object of the present invention, in described metal traps, the range of choices of the content of each component is wider, for the present invention, the lanthanide rare metal oxide containing the aluminium oxide with stepped pore distribution of 5-90 % by weight, the magnesia of 5-90 % by weight and 5-20 % by weight in preferred described metal traps and/or transition metal oxide; More preferably the aluminium oxide with stepped pore distribution containing 20-70 % by weight in described metal traps, the magnesia of 20-70 % by weight, the lanthanide rare metal oxide of 8-15 % by weight and/or transition metal oxide.
According to metal traps of the present invention, according to needing, also containing Four composition in described metal traps, described Four composition can for except described magnesia, described in there is heat-resistant inorganic oxide except the aluminium oxide of stepped pore distribution and described lanthanide rare metal oxide and/or transition metal oxide and/or clay.The range of choices of the content of described Four composition is wider, specifically can select according to actual needs, the present invention to this without particular/special requirement, general with the gross weight of metal traps for benchmark, the content of described Four composition is 0.001-30 % by weight, preferred, the described Four composition containing the aluminium oxide with stepped pore distribution of 10-90 % by weight, the magnesia of 5-60 % by weight, the lanthanide rare metal oxide of 8-15 % by weight and/or transition metal oxide and aequum in described metal traps.
According to metal traps of the present invention, the range of choices of the kind of described heat-resistant inorganic oxide is wider, meet the conventional heat-resistant inorganic oxide of the prior art of aforementioned claim (usually also referred to as binding agent oxide in this area) and all can be used for the present invention, for the present invention, preferred described heat-resistant inorganic oxide is selected from silica, one or more in the metal oxide (as zirconia, calcium oxide etc.) outside the described aluminium oxide had except the aluminium oxide of stepped pore distribution, magnesia and described lanthanide rare metal oxide and/or transition metal oxide.
According to metal traps of the present invention, the range of choices of the kind of described clay is wider, the clay that this area is commonly used all can be used for the present invention, for the present invention, preferred described clay be selected from kaolin, metakaolin, sepiolite, attapulgite, montmorillonite, tired de-stone, diatomite, galapectite, saponite, boron-moisten soil, hydrotalcite one or more, more preferably described clay to be selected from kaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone one or more.
According to metal traps of the present invention, the range of choices of the kind of described lanthanide rare metal oxide and/or transition metal oxide is wider, the lanthanide rare metal oxide that this area routine uses and/or transition metal oxide all can be used for the present invention, for the present invention, preferred described lanthanide rare metal oxide and/or transition metal oxide be selected from lanthana, titanium oxide and manganese oxide one or more.
The preparation method of metal traps described in the present invention can carry out with reference to prior art, it can adopt the method for this area routine to prepare, according to one embodiment of the present invention, the invention provides a kind of preparation method of metal traps, the method comprises:
(1) little porous aluminum oxide, macroporous aluminium oxide, deionized water and sour mixed pulp are obtained the first slurries;
(2) described first slurries are contacted with magnesium hydroxide and/or magnesia obtain the second slurries;
(3) roasting is carried out after described second slurries being carried out spraying dry;
Wherein, with the pore volume in 2-100nm hole for benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-35%, and the pore volume in 5-10nm hole accounts for 25-45%, and the pore volume in 10-60nm hole accounts for 20-50%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%;
Wherein, in order to lanthanide rare metal oxide and/or transition metal oxide are incorporated in metal traps of the present invention, can introduce in any one or more steps in step of the present invention (1), step (2) and step (3), namely any one or more steps in step of the present invention (1), step (2) and step (3) can be carried out under the existence of at least one lanthanide metal compound and/or at least one transistion metal compound, and method of the present invention can be undertaken by following any one or numerous embodiments particularly:
A: the mixed pulp of step (1) carries out under the existence of at least one lanthanide metal compound and/or at least one transistion metal compound;
B: the first slurries of step (2) and magnesium hydroxide and/or magnesian contact are carried out under the existence of at least one lanthanide metal compound and/or at least one transistion metal compound;
C: by after step (3) spraying dry and the solid obtained before roasting contact with at least one lanthanide metal compound and/or at least one transistion metal compound;
D: the solid obtained after step (3) roasting is contacted with at least one lanthanide metal compound and/or at least one transistion metal compound;
Also be, the mixed pulp of step of the present invention (1) and/or the first slurries of step (2) and magnesium hydroxide and/or magnesian contact are carried out under the existence of at least one lanthanide metal compound and/or at least one transistion metal compound, and/or contact by the solid obtained after step (3) spraying dry and/or by the solid obtained after step (3) roasting with at least one lanthanide metal compound and/or at least one transistion metal compound before roasting.
According to one of the present invention preferred embodiment, the invention provides a kind of preparation method of metal traps, the method comprises:
(1) little porous aluminum oxide, deionized water and sour mixed pulp are obtained the first slurries;
(2) described first slurries are contacted with magnesium hydroxide and/or magnesia obtain the second slurries;
(3) described second slurries are contacted with macroporous aluminium oxide obtain the 3rd slurries;
(4) roasting is carried out after described 3rd slurries being carried out spraying dry;
Wherein, with the pore volume in 2-100nm hole for benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-35%, and the pore volume in 5-10nm hole accounts for 25-45%, and the pore volume in 10-60nm hole accounts for 20-50%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%;
Wherein, in order to lanthanide rare metal oxide and/or transition metal oxide are incorporated in metal traps of the present invention, can in step of the present invention (1), step (2), introduce in any one or more steps in step (3) and step (4), i.e. step of the present invention (1), step (2), any one or more steps in step (3) and step (4) can be carried out under the existence of at least one lanthanide metal compound and/or at least one transistion metal compound, method of the present invention can be undertaken by following any one or numerous embodiments particularly:
A: the mixed pulp of step (1) carries out under the existence of at least one lanthanide metal compound and/or at least one transistion metal compound;
B: the first slurries of step (2) and magnesium hydroxide and/or magnesian contact are carried out under the existence of at least one lanthanide metal compound and/or at least one transistion metal compound;
C: step (3) the contact of described second slurries and macroporous aluminium oxide is carried out under the existence of at least one lanthanide metal compound and/or at least one transistion metal compound;
D: by after step (4) spraying dry and the solid obtained before roasting contact with at least one lanthanide metal compound and/or at least one transistion metal compound;
E: the solid obtained after step (4) roasting is contacted with at least one lanthanide metal compound and/or at least one transistion metal compound;
Also be, the mixed pulp of step of the present invention (1) and/or the first slurries of step (2) and magnesium hydroxide and/or magnesianly to contact and/or step (3) the contact of described second slurries and macroporous aluminium oxide is carried out under the existence of at least one lanthanide metal compound and/or at least one transistion metal compound, and/or contact by the solid obtained after step (4) spraying dry and/or by the solid obtained after step (4) roasting with at least one lanthanide metal compound and/or at least one transistion metal compound before roasting.
Preparation in accordance with the present invention, described macroporous aluminium oxide and little porous aluminum oxide are given an account of before this invention in the process of the metal traps of the present invention that continues and are described in detail, do not repeat them here.
Preparation in accordance with the present invention, carry out realizing object of the present invention according to preceding solution of the present invention, in preparation process, the range of choices of various material consumption is wider, for the present invention, the consumption of preferred described macroporous aluminium oxide and little porous aluminum oxide makes to contain 10-90 % by weight in the aluminium oxide in the metal traps prepared, the macroporous aluminium oxide of preferred 15-85 % by weight and 10-90 % by weight, the little porous aluminum oxide of preferred 15-85 % by weight, and total consumption of described macroporous aluminium oxide and little porous aluminum oxide makes the total content of macroporous aluminium oxide and little porous aluminum oxide in the metal traps prepared be 5-90 % by weight.
Preparation in accordance with the present invention, carry out realizing object of the present invention according to preceding solution of the present invention, in preparation process, the range of choices of various material consumption is wider as previously mentioned, for the present invention, preferred described magnesium hydroxide and/or magnesian consumption make the magnesia containing 5-90 % by weight in the metal traps prepared.
Preparation in accordance with the present invention, carry out realizing object of the present invention according to preceding solution of the present invention, described in step (1), the range of choices of the condition of mixed pulp is wider, specifically can carry out with reference to prior art, the consumption for acid in preferred steps of the present invention (1) makes the pH value of the first slurries be 1-3.0; The consumption of step (1) medium and small porous aluminum oxide and/or at least one lanthanide metal compound and/or at least one transistion metal compound and deionized water makes the solid content of the first slurries be 8-20 % by weight.
Preparation in accordance with the present invention, carry out realizing object of the present invention according to preceding solution of the present invention, described in step (2), the range of choices of the condition of contact is wider, for the present invention, described in preferred steps (2), the condition of contact comprises: temperature is 0-70 DEG C, is preferably 15-60 DEG C; Time is more than 15min, is preferably 15-90min.Preparation in accordance with the present invention, carry out realizing object of the present invention according to preceding solution of the present invention, described in step (3), the range of choices of the condition of contact is wider, for the present invention, described in preferred steps (3), the condition of contact comprises: temperature is 10-60 DEG C, and the time is 20-60min.Preparation in accordance with the present invention, the range of choices of the kind of described lanthanide element and/or transition metal is wider, the lanthanide element that this area routine uses and/or transition metal all can be used for the present invention, for the present invention, preferred described lanthanide element and/or transition metal be selected from lanthanum, titanium and manganese one or more; In the present invention, the range of choices of the kind of described at least one lanthanide metal compound and/or at least one transistion metal compound is wider, specifically can be selected from the chloride of lanthanide series metal, the hydroxide of lanthanide series metal, the carbonate compound of lanthanide series metal, the hydroxide of transition metal, the chloride of transition metal, the carbonate compound of transition metal.In the present invention, the consumption of preferred described at least one lanthanide metal compound and/or at least one transistion metal compound makes the lanthanide rare metal oxide and/or the transition metal oxide that contain 5-20 % by weight in the metal traps prepared.
Preparation in accordance with the present invention, according to needing to introduce the 4th material in the process of the described metal traps of preparation, particularly such as can the mixed pulp of step (1) and/or step (2) by described first slurries and magnesium hydroxide and/or magnesian contact and/or step (3) introduce the 4th material by the contact process of described second slurries and macroporous aluminium oxide, also the solid contact that described 4th material and step (4) roasting obtain can be introduced by load; For the present invention, the mixed pulp of preferred steps (1) and/or step (2) by described first slurries and magnesium hydroxide and/or magnesianly to contact and/or step (3) the contact of described second slurries and macroporous aluminium oxide is carried out under the 4th material exists, wherein, described 4th material is clay, one or more in the heat-resistant inorganic oxide except magnesia, described macroporous aluminium oxide, described little porous aluminum oxide, described magnesium hydroxide, described lanthanide metal compound and/or transistion metal compound and/or the presoma of heat-resistant inorganic oxide.
According to one of the present invention preferred embodiment, total consumption of described macroporous aluminium oxide and little porous aluminum oxide, described magnesium hydroxide and/or magnesian consumption, described at least one lanthanide metal compound and/or the consumption of at least one transistion metal compound and the consumption of described 4th material make to contain the macroporous aluminium oxide of 10-90 % by weight and little porous aluminum oxide in the metal traps prepared, the oxide of described 4th material of the magnesia of 5-60 % by weight, the lanthanide rare metal oxide of 8-15 % by weight and/or transition metal oxide and aequum.
Preparation in accordance with the present invention, the kind of described clay and heat-resistant inorganic oxide is described in detail in the part of foregoing description metal traps of the present invention, and at this, it is no longer repeated.
Preparation in accordance with the present invention, the range of choices of the kind of described heat-resistant inorganic oxide presoma is wider, the heat-resistant inorganic oxide presoma (this area is also referred to as binding agent) that this area meeting aforementioned claim is commonly used all can be used for the present invention, for the present invention, preferred described heat-resistant inorganic oxide presoma be selected from Ludox, waterglass, boehmite, Alumina gel and silicon-aluminum sol one or more.
Preparation in accordance with the present invention, the method for described spraying dry, drying, roasting all can refer to prior art and carries out, the present invention to this without particular/special requirement.
The invention provides a kind of metal traps prepared according to preparation method of the present invention.
The invention provides the application of metal traps of the present invention in catalytic cracking.
Metal traps of the present invention has good metal trapping effect, metal traps provided by the invention is used for high vanadium RFCC, can slows down the destruction of vanadium to Cracking catalyst, improve liquid product yield, reduce dry gas and coking yield.Such as, when metal traps provided by the invention mixes by weight for 3:97 with industrial cracking catalyst, on catalyst mixture, Ni content is about 2000ppm, content of vanadium is when being about 4500ppm, with be used alone compared with industrial cracking catalyst, heavy oil yield is reduced to 10.36 % by weight by 12.36 % by weight, total liquid product yield is increased to 74.15 % by weight by 71.60 % by weight, and dry gas selectivity is down to 0.0338 by 0.0358, and coke selectivity is down to 0.1798 by 0.1910.As can be seen here, heavy oil transformation more effectively can be become high-value product by metal traps provided by the invention.
The invention provides a kind of catalyst cracking method, the method comprises: under catalytic cracking condition, contacted with the catalyst mixture of catalytic cracking catalyst with containing metal traps by heavy oil feedstock, wherein, described metal traps is metal traps of the present invention.
According to catalyst cracking method of the present invention, in preferred described catalyst mixture, the weight ratio of metal traps and catalytic cracking catalyst is 1:4-99, is preferably 1:5.7-99, is more preferably 1:6-32.
According to catalyst cracking method of the present invention, the catalytic cracking condition that described catalytic cracking condition can be commonly used for this area, the present invention, is not described in detail at this without particular/special requirement this.
In the present invention, if not otherwise specified, ppm is ppm by weight.
Below by embodiment, the present invention is further described, but not thereby limiting the invention.
In the present invention, the weight of roasting after 1 hour under the condition of about 800 DEG C is referred in the weight of butt.
In the present invention, the solid content of material refers to the weight of material after high-temperature roasting and the weight ratio before roasting, i.e. the water content % of the solid content=100%-material of material.
In the present invention, oil ratio refers to the mass ratio of catalyst and feedstock oil.
In an embodiment with in comparative example:
Alumina gel provides (Al by catalyst asphalt in Shenli Refinery of China Petrochemical Industry
2o
3content is 21.5 % by weight), kaolin originates from Chinese Suzhou (solid content is 76.9 % by weight), and boehmite is provided (solid content is 60.8 % by weight) by Shandong Aluminum Plant, and magnesia effluent Bei Meishen Chemical Co., Ltd. provides.Industrial catalyst C(trade mark HGY) provided by Sinopec Shandong catalyst branch company, in comparative example and embodiment, chemical reagent used does not indicate especially, and its specification is chemical pure.
In embodiments, abrasion index and bulk density adopt RIPP standard method to measure (see " Petrochemical Engineering Analysis method (RIPP experimental technique) ", the volumes such as Yang Cuiding, Science Press, nineteen ninety publication).In catalyst mixture, Ni, V content x-ray fluorescence method measures; The thing of metal traps adopts XRD method to measure mutually.
Embodiment 1
The present embodiment is for illustration of the preparation process of metal traps provided by the invention.
(1) little porous aluminum oxide A190g(is pressed Al
2o
3meter) add in deionized water, after being uniformly dispersed, add lanthanum carbonate (containing La
2o
350 grams), after being uniformly dispersed, then add hydrochloric acid, contact and obtain the first slurries after 30 minutes, the pH value of the first slurries is 1.1, and solid content is 15 % by weight;
(2) then add the MgO slurries (containing MgO700g) of deionized water dispersion, temperature obtains the second slurries after controlling to contact 60 minutes at 55 DEG C, and the pH value of the second slurries is 8.9, and solid content is 28 % by weight;
(3) macroporous aluminium oxide A60g(is then added by Al
2o
3meter) obtain the 3rd slurries, at 10-40 DEG C, contact 15min;
(4) by roasting direct after the 3rd slurries spray drying forming, roasting condition is 600 DEG C/2h, obtains metal traps A1;
Wherein, (the pore size distribution figure of macroporous aluminium oxide A, little porous aluminum oxide A is shown in Fig. 1) in table 1 is listed in the pore size distribution of aluminium oxide, and the formula of A1, preparation parameter and abrasion index are listed in table 2.The XRD spectra of A1 is shown in Fig. 4, and as seen from Figure 4, containing magnesia-alumina spinel structure in metal traps A1, namely in metal traps, at least part of magnesia and aluminium oxide define magnesia-alumina spinel structure;
Wherein, metal traps A1 fresh state and in 800 DEG C, the pore size distribution figure of hydrothermal aging after 17 hours is shown in Fig. 2 under 100% water vapour atmosphere; Metal traps A1 mesopore after hydrothermal aging remains intact as seen from Figure 2, and provides larger pore volume.
Embodiment 2-8
Example 2-8 is for illustration of the preparation process of metal traps provided by the invention.
Prepare metal traps A2-A8 according to the method for embodiment 1, list in table 2 unlike formula, preparation parameter and abrasion index.
Embodiment 9
Metal traps A9 is prepared according to the method for embodiment 1, unlike, do not have step (3), and directly added in step (1) together with little porous aluminum oxide by macroporous aluminium oxide, all the other Step By Conditions are all identical, obtain metal traps A9.
Comparative example 1
This comparative example is for illustration of the preparation process of contrast metal traps B1.
(1) boehmite 250g(is pressed Al
2o
3meter), lanthanum hydroxide is (with La
2o
3meter, 50g) add in deionized water, after being uniformly dispersed, add hydrochloric acid, contact and obtain the first slurries after 30 minutes, the pH value of the first slurries is 1.5, and solid content is 15 % by weight;
(2) then add the MgO slurries (containing MgO700g) of deionized water dispersion to described first slurries, obtain the second slurries contact 60 minutes at 74 DEG C after, the pH value of the second slurries is 9.9, and solid content is 28 % by weight;
By the second slurries spray drying forming, roasting direct, roasting condition is 600 DEG C/2h, obtains metal traps B1.The formula of B1, preparation parameter and abrasion index are listed in table 3.The XRD spectra of B1 is shown in Fig. 4, and as seen from Figure 4, containing magnesia-alumina spinel structure in metal traps A1, namely in metal traps, at least part of magnesia and aluminium oxide define magnesia-alumina spinel structure;
Wherein, metal traps B1 fresh state and in 800 DEG C, the pore size distribution figure of hydrothermal aging after 17 hours is shown in Fig. 3 under 100% water vapour atmosphere; Substantially mesopore is not formed as seen from Figure 3 after metal traps B1 hydrothermal aging.
Comparative example 2-4
According to the method preparation contrast metal traps B2-B4 of comparative example 1, unlike, the formula of B2, B3, B4, preparation parameter and abrasion index are listed in table 3.From abrasion index, only use contrast auxiliary agent B 3 intensity difference of macroporous aluminium oxide, be not suitable for catalytic cracking process.
Table 1
Embodiment 10-18
Embodiment 10-18 is used for the Catalytic Cracking Performance of catalytic cracking for illustration of the heavy metal-polluted dyeing method of metal traps and industrial cracking catalyst mixture and metal traps of the present invention.
First the solid content of analytical industry Cracking catalyst C and metal traps A1-A9 provided by the invention, then catalyst mixture is obtained with butt metering physical mixed, catalyst mixture first carries out cyclic polluting (to deposit Ni and V) on circulation aging equipment, on catalyst mixture after cyclic polluting, Ni, V content is in table 5 and table 6, wherein
Cycle is polluted step and is comprised: after catalyst mixture introduces heavy metal (Ni and V) by meter Xie Er infusion process, then the catalyst mixture introduced after heavy metal is loaded in D-100 device (small fixed flowing bed), D-100 device processes as follows:
A () in a nitrogen atmosphere, with the heating rate of 20 DEG C/min, is heated to 600 DEG C;
B (), with the heating rate of 1.5 DEG C/min, after being heated to 780 DEG C, constant temperature, at 780 DEG C, changes process atmosphere in thermostatic process as follows:
(i) with the nitrogen (wherein, the propylene containing 5 volume % in nitrogen) containing 40 volume %, the atmosphere process of the steam of 60 volume % 10 minutes,
(ii) with the nitrogen (pure nitrogen gas, without propylene) containing 40 volume %, the atmosphere process of the steam of 60 volume % 10 minutes,
(iii) to contain the air of 40 volume % (containing 4000 μm of ol/molSO
2), the atmosphere process of the steam of 60 volume % 10 minutes,
(iv) with the nitrogen containing 40 volume %, the atmosphere process of the steam of 60 volume % 10 minutes; Then press aforementioned sequence again repetitive cycling step (i)-(iv) respectively once then repeat step (i), end loop pollutes step;
Then carry out aging step: the catalyst mixture after cyclic polluting at 788 DEG C, in containing the atmosphere of the steam of 80 volume % and the air of 20 volume % aging 8 hours;
Then on ACE device, investigate the catalytic performance of the catalyst mixture after cyclic polluting-aging, wherein, feedstock oil enters in reactor bottom and contacts with catalyst mixture, wherein, raw materials used oil nature in table 4, appreciation condition and the results are shown in Table 5 and table 6.
Comparative example 5-8
Comparative example 5-8 is used for the Catalytic Cracking Performance of catalytic cracking for illustration of the heavy metal-polluted dyeing method of comparative catalyst's mixture and contrast metal traps.
According to the method for embodiment 10-18 carry out metallic pollution and and catalytic cracking, the auxiliary agent B 4 that the auxiliary agent B 2 that the auxiliary agent B 1, the comparative example 2 that provide for independent industrial catalyst C, comparative example 1 unlike the catalyst mixture adopted provide, comparative example 4 provide and the catalyst mixture of industrial catalyst C after physical mixed, to pollute on rear catalyst mixture Ni, V content in table 5 and table 6, appreciation condition and the results are shown in Table 5 and table 6.
Table 4
As can be seen from the data of table 5, in catalytic cracking catalyst, add metal traps provided by the invention can slow down the destruction of vanadium to catalytic cracking catalyst, improve the selective of coke and dry gas, increase total liquid product yield, simultaneously, from dry gas yield, metal traps of the present invention also has the effect of certain anti-nickel contamination.
Table 6
As can be seen from the data of table 6, metal traps provided by the invention has better vanadium trapping ability, for more effectively improving the selective of coke and dry gas in catalytic cracking process, increases total liquid product yield.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each the concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, can be combined by any suitable mode.
In addition, also can be combined between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (17)
1. a preparation method for metal traps, wherein, the method comprises:
(1) little porous aluminum oxide, deionized water and sour mixed pulp are obtained the first slurries;
(2) described first slurries are contacted with magnesium hydroxide and/or magnesia obtain the second slurries;
(3) described second slurries are contacted with macroporous aluminium oxide obtain the 3rd slurries;
(4) roasting is carried out after described 3rd slurries being carried out spraying dry;
Wherein, with the pore volume in 2-100nm hole for benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-35%, and the pore volume in 5-10nm hole accounts for 25-45%, and the pore volume in 10-60nm hole accounts for 20-50%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%;
Wherein, the mixed pulp of step (1) and/or the first slurries of step (2) and magnesium hydroxide and/or magnesianly to contact and/or step (3) the contact of described second slurries and macroporous aluminium oxide is carried out under the existence of at least one lanthanide metal compound and/or at least one transistion metal compound, and/or contact by the solid obtained after step (4) spraying dry and/or by the solid obtained after step (4) roasting with at least one lanthanide metal compound and/or at least one transistion metal compound before roasting;
Wherein, the consumption of described macroporous aluminium oxide and little porous aluminum oxide makes containing the macroporous aluminium oxide of 10-90 % by weight and the little porous aluminum oxide of 10-90 % by weight in the aluminium oxide in the metal traps prepared, and total consumption of described macroporous aluminium oxide and little porous aluminum oxide makes the total content of macroporous aluminium oxide and little porous aluminum oxide in the metal traps prepared be 5-90 % by weight;
Wherein, described magnesium hydroxide and/or magnesian consumption make the magnesia containing 5-90 % by weight in the metal traps prepared;
Wherein, the consumption of described at least one lanthanide metal compound and/or at least one transistion metal compound makes the lanthanide rare metal oxide and/or the transition metal oxide that contain 5-20 % by weight in the metal traps prepared.
2. preparation method according to claim 1, wherein,
In step (1), the consumption of acid makes the pH value of the first slurries be 1-3.0;
The consumption of step (1) medium and small porous aluminum oxide and/or at least one lanthanide metal compound and/or at least one transistion metal compound and deionized water makes the solid content of the first slurries be 8-20 % by weight.
3. preparation method according to claim 1 and 2, wherein, described in step (2), the condition of contact comprises: temperature is 0-70 DEG C, and the time is more than 15min.
4. preparation method according to claim 1 and 2, wherein, described in step (3), the condition of contact comprises: temperature is 10-60 DEG C, and the time is 2-20min.
5. preparation method according to claim 1 and 2, wherein, described lanthanide element and/or transition metal be selected from lanthanum, titanium and manganese one or more; Described at least one lanthanide metal compound and/or at least one transistion metal compound are selected from chloride, the hydroxide of lanthanide series metal, the carbonate compound of lanthanide series metal, the hydroxide of transition metal, the chloride of transition metal, the carbonate compound of transition metal of lanthanide series metal.
6. preparation method according to claim 1 and 2, wherein, the mixed pulp of step (1) and/or step (2) by described first slurries and magnesium hydroxide and/or magnesianly to contact and/or step (3) the contact of described second slurries and macroporous aluminium oxide is carried out under the 4th material exists, described 4th material is clay, except magnesia, described macroporous aluminium oxide, described little porous aluminum oxide, described magnesium hydroxide, one or more in heat-resistant inorganic oxide beyond described lanthanide metal compound and/or transistion metal compound and/or the presoma of heat-resistant inorganic oxide.
7. preparation method according to claim 6, wherein, total consumption of described macroporous aluminium oxide and little porous aluminum oxide, described magnesium hydroxide and/or magnesian consumption, the consumption of described at least one lanthanide metal compound and/or at least one transistion metal compound and the consumption of described 4th material make to contain the macroporous aluminium oxide of 10-90 % by weight and little porous aluminum oxide in the metal traps prepared, the magnesia of 5-60 % by weight, the oxide of described 4th material of the lanthanide rare metal oxide of 8-15 % by weight and/or transition metal oxide and aequum.
8. preparation method according to claim 6, wherein, described heat-resistant inorganic oxide presoma be selected from Ludox, waterglass, boehmite, Alumina gel and silicon-aluminum sol one or more.
9. the metal traps prepared by the preparation method in claim 1-6 and 8 described in any one, this metal traps contains lanthanide rare metal oxide and/or the transition metal oxide of the aluminium oxide with stepped pore distribution of 5-90 % by weight, the magnesia of 5-90 % by weight and 5-20 % by weight, and aluminium oxide and at least part of magnesia form magnesia-alumina spinel structure at least partly;
Wherein, the aluminium oxide described in stepped pore distribution contains the macroporous aluminium oxide of 10-90 % by weight and the little porous aluminum oxide of 10-90 % by weight; With the pore volume in 2-100nm hole for benchmark, in described macroporous aluminium oxide, the pore volume in 2-5nm hole accounts for 20-35%, and the pore volume in 5-10nm hole accounts for 25-45%, and the pore volume in 10-60nm hole accounts for 20-50%; In described little porous aluminum oxide, the pore volume in 2-5nm hole accounts for 50-70%, and the pore volume in 5-10nm hole accounts for 15-30%, and the pore volume in 10-60nm hole accounts for 10-20%.
10. metal traps according to claim 9, wherein, also containing Four composition in described metal traps, described Four composition for except described magnesia, described in there is heat-resistant inorganic oxide except the aluminium oxide of stepped pore distribution and described lanthanide rare metal oxide and/or transition metal oxide and/or clay.
11. metal traps according to claim 10, wherein, the described Four composition containing the aluminium oxide with stepped pore distribution of 10-90 % by weight, the magnesia of 5-60 % by weight, the lanthanide rare metal oxide of 8-15 % by weight and/or transition metal oxide and aequum in described metal traps.
12. metal traps according to claim 10, wherein, described heat-resistant inorganic oxide is selected from silica, one or more in the metal oxide outside the described aluminium oxide had except the aluminium oxide of stepped pore distribution, magnesia and described lanthanide rare metal oxide and/or transition metal oxide.
13. metal traps according to claim 10, wherein, described clay to be selected from kaolin, diatomite, sepiolite, attapulgite, montmorillonite and tired de-stone one or more.
14. according to the metal traps in claim 9-13 described in any one, wherein, described lanthanide rare metal oxide and/or transition metal oxide be selected from lanthana, titanium oxide and manganese oxide one or more.
The application of metal traps in 15. claim 9-14 described in any one in catalytic cracking.
16. 1 kinds of catalyst cracking methods, the method comprises: under catalytic cracking condition, contacted with the catalyst mixture of catalytic cracking catalyst with containing metal traps by heavy oil feedstock, it is characterized in that, described metal traps is the metal traps in claim 9-14 described in any one.
17. methods according to claim 16, wherein, in described catalyst mixture, the weight ratio of metal traps and catalytic cracking catalyst is 1:4-99.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210420770.2A CN103785346B (en) | 2012-10-29 | 2012-10-29 | A kind of metal traps and its preparation method and application and a kind of catalyst cracking method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210420770.2A CN103785346B (en) | 2012-10-29 | 2012-10-29 | A kind of metal traps and its preparation method and application and a kind of catalyst cracking method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103785346A CN103785346A (en) | 2014-05-14 |
| CN103785346B true CN103785346B (en) | 2016-04-27 |
Family
ID=50661654
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210420770.2A Active CN103785346B (en) | 2012-10-29 | 2012-10-29 | A kind of metal traps and its preparation method and application and a kind of catalyst cracking method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103785346B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106378204A (en) * | 2016-08-12 | 2017-02-08 | 青岛惠城环保科技股份有限公司 | Preparation method for metal capturing agent |
| CN106378203B (en) * | 2016-08-12 | 2020-01-14 | 青岛惠城环保科技股份有限公司 | Preparation method of metal trapping agent |
| CN106435210A (en) * | 2016-09-27 | 2017-02-22 | 宁波大地化工环保有限公司 | Preparation method of trapping agent special for precious metal |
| CN106732696B (en) * | 2016-12-01 | 2019-04-05 | 中国石油大学(华东) | A kind of magnesium aluminate spinel compoud and its application being enclosed with silicon phosphorus aluminium layer |
| CN114426865B (en) * | 2020-09-24 | 2023-09-05 | 中国石油化工股份有限公司 | Method for reducing metal content in oil product and application |
| CN114426872B (en) * | 2020-09-25 | 2023-09-05 | 中国石油化工股份有限公司 | Catalytic conversion method for inferior crude oil |
| CN113802014B (en) * | 2021-08-25 | 2022-08-05 | 中南大学 | Method for recovering platinum group metal in alumina-based waste catalyst by pyrogenic process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5603823A (en) * | 1995-05-12 | 1997-02-18 | W. R. Grace & Co.-Conn. | LA/ND-spinel compositions for metals passivation in FCC processes |
| CN1491188A (en) * | 2001-02-09 | 2004-04-21 | ŵ�����˹ɷ�����˾ | Doped anionic clays |
| CN101583696A (en) * | 2006-12-06 | 2009-11-18 | 哥伦比亚国家石油股份有限公司 | Vanadium traps for catalytic cracking processes and preparation thereof |
| CN101745417A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
-
2012
- 2012-10-29 CN CN201210420770.2A patent/CN103785346B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5603823A (en) * | 1995-05-12 | 1997-02-18 | W. R. Grace & Co.-Conn. | LA/ND-spinel compositions for metals passivation in FCC processes |
| CN1491188A (en) * | 2001-02-09 | 2004-04-21 | ŵ�����˹ɷ�����˾ | Doped anionic clays |
| CN101583696A (en) * | 2006-12-06 | 2009-11-18 | 哥伦比亚国家石油股份有限公司 | Vanadium traps for catalytic cracking processes and preparation thereof |
| CN101745417A (en) * | 2008-11-28 | 2010-06-23 | 中国石油化工股份有限公司 | Catalytic cracking catalyst |
Non-Patent Citations (2)
| Title |
|---|
| 镁铝尖晶石作为催化裂化双功能助剂的研究;李晓 等;《石油学报（石油加工）》;20010630;第17卷(第3期);第57-61页 * |
| 镧、磷复合添加组分对催化裂化催化剂;朱玉霞 等;《石油学报（石油加工）》;20030831;第19卷(第4期);第8-14页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103785346A (en) | 2014-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103785346B (en) | A kind of metal traps and its preparation method and application and a kind of catalyst cracking method | |
| Mokaya et al. | Pillared clays and pillared acid-activated clays: a comparative-study of physical, acidic, and catalytic properties | |
| CN105126928B (en) | A kind of preparation method of modified mesoporous silica-alumina materials | |
| CN1915486B (en) | Hydrated alumina with structure of similar to thin diaspore of containing additive | |
| CN1915485B (en) | Alumina containing additive | |
| CN104226234A (en) | Metal trapping agent and catalytic cracking method | |
| CN103789013B (en) | A kind of metal traps and its preparation method and application and a kind of catalyst cracking method | |
| CN101451074A (en) | Catalyst for heavy oil catalytic cracking and preparation method thereof | |
| CN105214669A (en) | A kind of efficient attapulgite clay is catalyst based and preparation method thereof | |
| Silva et al. | Effect of the chemical composition of smectites used in KF/Clay catalysts on soybean oil transesterification into methyl esters | |
| CN107344720B (en) | A kind of Y type molecular sieve and preparation method thereof | |
| CN103769076B (en) | Method for preparing olefin-removal catalyst by taking clay as raw materials | |
| CN103785428A (en) | Metal chelating agent, preparation method and application thereof, and catalytic cracking method | |
| Liu et al. | Vanadium contamination on the stability of zeolite USY and efficient passivation by La2O3 for cracking of residue oil | |
| CN103785427B (en) | A kind of metal traps and its preparation method and application and a kind of catalyst cracking method | |
| CN104556081A (en) | Modified kaolin as well as preparation method and application thereof | |
| CN102806096B (en) | Rare earth-containing Y-type molecular sieve cracking catalyst and preparation method thereof | |
| CN103706353A (en) | AlMn composite pillared clay supported CrCe catalyst, and preparation method and application of catalyst | |
| CN103789014B (en) | A kind of metal traps and its preparation method and application and a kind of catalyst cracking method | |
| CN102786064B (en) | Hydrocracking catalyst carrier and preparation method thereof | |
| CN103785370B (en) | A kind of metal traps and its preparation method and application and a kind of catalyst cracking method | |
| CN107344102B (en) | A kind of hydrocracking catalyst and its preparation method | |
| CN104226235A (en) | Metal trapping agent and catalytic cracking method | |
| CN105536689B (en) | A kind of supported dearsenic agent and preparation method thereof | |
| Wang et al. | Simple preparation of high concentration Nd3+-modified NaY zeolites with lower desorption activation energy of water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |